Production of nitriles



- Patented Oct. 5, 1948 OFFICE raonuc'rron or Nrramas William I. Denton, Woodbury, and Richard B.

Bishop, Haddonfleld, N. .L, assignors to Socony- Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application May 24, 1946,

. Serial No. 672,154

- 12 Claims. 1

This invention relates to a process for producing nitriles having at least two carbon atoms, and is more particularly concerned with a'catalytic process for producing nitriles having at least two carbon atoms, from parafilnic hydrocarbons.

Nitriles are organic compounds containing combined nitrogen. Their formula may be represented thus: R-CEN, in which R is an alkyl or an aryl group. 'These compounds are very useful since they can be converted readily to many valuable products such as acids, amines, aldehydes, esters, etc.

As is well known to those familiar with the art, several processes have been proposed for the preparation of nitriles. In general, however, all of these processes have been disadvantageous from one or more standpoints, namely, the relaaromatic sulfonates or with aromatic substituted alkyl halides; by reacting more complex cyanides,

such as potassium cuprous cyanide, with diazonium halides; by reacting isothiocyanates with copper or with zinc dust; and by reacting aryl aldoximes with acyl halides.

We have now found a process for producing nitriles which is simple and inexpensive, and which employs non-toxic reactants.

We have discovered that nitriles containing at least two carbon atoms can be prepared by reacting paraffinic hydrocarbons having at least two.

carbon atoms, with ammonia, at elevated temper-- atures, in the presence of catalytic material containing vanadium oxide.

Our invention is to be distinguished from the conventional processes for the production of hydrogen cyanide wherein carbon compounds, such as carbon monoxide, methane, and benzene, are reacted with ammonia, at elevated temperatures in the presence of alumina, nickel, quartz, clays, oxides of thorium and cerium, copper, iron oxide, silver, iron, cobalt, chromium, aluminum phosphate, etc. The process of the present invention is also tov be distinguished from the processes of the prior art for the production of amines wherein hydrocarbons are reacted with ammonia at high temperatures, or at lower temperatures in the presence of nickel.

Accordingly, it is an object of the present invention to provide a process for the production "of nitriles containing at least two carbon atoms. Another object is to ailord a catalytic process for the production of nitriles containing at least two carbon atoms. An important object is to provide a process for producing nitriles containing at least two carbon atoms which is inexpensive and commercially feasible. A specific object is to provide a process for producing nitriles containing at least two carbon atoms from paraflinic hydrocarbons having at least two carbon atoms. Other objects and advantages of the present invention will become apparent to those skilled in the art from the following description.

Broadly stated, our invention provides an inexpensive and commercially feasible process for the production of nitriles containing at least two carbon atoms, which comprises reacting a paraffinic hydrocarbon having at least two carbon atoms, with ammonia, in the gaseous phase and at elevated temperatures, in-the presence of catalytic material containing vanadium oxide.

Generally speaking, any paraflinic hydrocarbon having at least two carbon atoms is suitable as the hydrocarbon reactant in the process of our invention. Ethane, propane, pentane, butane, isobutane, hexane, methyl hexane, dimethyl pentane, heptane, cetane, octadecane, etc. may be mentioned by way of-non-limiting examples. It will be clear from the discussion of reaction temperatures set forth hereinafter, that many parafilnic hydrocarbons are not present per se when in contact with ammonia and a catalyst 01' the type used herein, for many of them are cracked to related hydrocarbons under such conditions. Nevertheless, all paraflinic hydrocarbons having at least two carbon atoms, and their hydrocarbon decomposition products, which are in the vapor phase under the hereindefined reaction conditions serve the purposes of the present invention. It is to be understood also, that hydrocarbon mixtures containing one or more parafllnic hydrocarbons having at least two carbon atoms, may also be used herein, and that when-such mixtures are used, the reaction conditions, such as contact time, will be slightly difierent in view of the dilution effect of the constituents present with, the parafiinic hydrocarbon or hydrocarbons having at least two carbonatoms. Accordingly, parafflnic hydrocarbons having at least two carbon atoms, mixtures thereof, and hydrocarbon mixtures containing one or more of such parafllnic hydrocarbons may be used.

Although any paramnic hydrocarbon having at least two carbon atoms may be utilized in our process, we especially prefer to use those contalning between two and about ten carbon atoms, and of these, propane, butane and heptane are especially preferred.

The proportions of reactants, i. e., parafilnic hydrocarbon having at least two carbonatoms a and ammonia, used in our process may be varied over a wide range with little effect on the conversion per pass and ultimate yield. In general, the charge of reactants may contain as little as 2 mol, percent or as much as 98 moi. percent of paraflinic hydrocarbons. In practice, however, we use charges containing between about 20 mol. percent and about 90 mol. percent of paraflinic hydrocarbon, and ordinarily, we prefer to use charges containing a molar excess oi! ammonia over the paraflinic hydrocarbon reactant.

We have found that the catalysts to be used to produce nitriles containing at least two carbon atoms, by reacting paraflinic hydrocarbons having at least two carbon atoms with ammonia, are

. those containing a vanadium oxide, such as vanadium monoxide (V) vanadium trioxide .(V203), vanadium dioxide (V02) and vanadium pentoxide (V20s).' Therefore, and in the interest of brevity, it must be clearly understood that when we speak of vanadium oxide, herein and in the claims, we have reference to the various oxides of vanadium. We have found, however, that vanadium pentoxide is to be preferred as a starting catalytic material.

While vanadium oxide catalysts are effective when used per se, they generally possess additional catalytic activity when used in conjunction with the well known catalyst supports, such as alumina, silica gel, carborundum, pumice, clays, and the like. We especially prefer to use alumina (A1203) as a catalyst support, and we have found that a catalyst comprising vanadium pentoxide supported on alumina is particularly useful for our purpose. Without any intent of limiting the scope of the present invention, it is suspected that the enhanced catalytic activity of the supported catalysts is attributable pri marily to their relatively large surface area.

The concentration of vanadium oxide in the supported catalysts influences the conversion per pass. In general, the conversion per pass increases with increase in the concentration of vanadium oxide. For example, we have found that a catalyst comprising 20 parts by weight of vanadium pentoxide on 80 parts by weight of alumina is more effective than one comprising parts by weight of vanadium pentoxide on 90 parts by weight of alumina. It is to be understood, however, that supported catalysts containing larger or smaller amounts of vanadium oxide may be used in our process. 7

We have found also that in order to obtain initial maximum catalytic efficiency, particularly where the catalytic material comprises the higher oxides oi vanadium, that the catalysts should be conditioned prior to use in the process. As defined herein, conditioned catalysts are those which have been exposed to ammonia or hydrogen, or both, for a period of time, several minutes to several hours, depending upon the quantity, at temperatures varying between about 800 F. and about 1300 F. However, ifdesired, the conditioning treatment may be dispensed with inasmuch as the catalyst becomes conditioned during the initial stages of our process when the catalyst comes in contact with the ammonia reactant.

In operation, the catalysts become fouled with carbonaceous material which ultimately affects their catalytic activity. Accordingly, when the emciency of the catalyst declines to a point where further operation becomes uneconomical or disadvantageous from a practical standpoint, the catalyst may be regenerated, as is well known in the art, by subjecting the same to a careful oxidation treatment, for example, by passing a stream of air or air diluted with flue gases over the catalyst under appropriate temperature conditions and for a suitable period of time, such as the same period of time as the catalytic operation. Preferably, the oxidation treatment is followed by a purging treatment. such as passing over the catalyst a stream of purge gas, for example, nitrogen, carbon dioxide, hydrocarbon ases, etc.

The reaction or contact time, i. e., the period of time during which a unit volume of the reactants is in contact with a unit volume of catalyst, may vary between a fraction of a second and several minutes. Thus, the contact time may be as low as 0.01 second and as high as 20 minutes. We prefer to use contact times varying between 0.1 second and one minute, particularly, between 0.3 second and 30 seconds.

In general, the temperatures to be used in our process vary between about 850 F. and up to the decomposition temperature of ammonia (about l250-'l300 F.), and preferably, temperatures varying between about 925 F. and about 1075 F. The preferred temperature to be used in any particular operation will depend upon the nature of the parafiln-ic hydrocarbon reactant used and upon the type of catalyst employed. Generally speaking, the higher temperatures increase the conversion per pass, but they also increase the decomposition of the reactants, thereby decreasing the ultimate yields of nitriles. Accordingly, the criteria for determining the optimum temperature to be used in any particular operation will be based on the nature of the paraffinic hydrocarbon reactant, the type of catalyst, and a consideration of commercial feasibility from the standpoint of striking a practical balance between conversion per pass and losses to decomposition. 4

The process of the present invention may be carried out at subatmospheric, atmospheric or superatmospheric pressures. Superatmospheric pressures are advantageous in that the unreacted charge materials condense more readily. Subatmospheric pressures appear to favor the reactions involved since the reaction products have a larger volume than the reactants, and hence, it is evident from the law of Le Chatelier-Braun that the equilibrium favors nitrile formation more at reduced pressures. However, such pressures reduce the throughput of the reactants and present increased dimculties in recycling unreacted charge materials. Therefore, atmospheric pressure or superatmospherio pressures are preferred.

At the present time, the reaction mechanism involved in the process of the present invention is not fully understood. Fundamentally, the simplest possible method of making nitriles is to introduce nitrogen directly into a hydrocarbon molecule, thereby avoiding intermediate steps with their accompanying increased cost. In our process, we have noted that considerable amounts of hydrogen are evolved; that when paramnic hydrocarbons higher than ethane are employed. aliphatic nitriles having fewer carbon atoms than the p'arafllnic hydrocarbon reactant predominate in the reaction product; and that when parai'ilnic hydrocarbons having at least six car-4 bon atoms in a straight chain are employed, aromatic nitriles as well as aliphatic nitriles are formed. Hence it is postulated, without any intent of limiting the scope of the present invention, that in our process, the aliphatic nitriles are formed in accordance with the following equations, using butane as an example:

or by formation of the corresponding alefinic hydrocarbon followed by the replacement of hydrogen with nitrogen therein; and that the arcmatic nitriles are formed by cyclization of the parafilnic hydrocarbons having at least six carbon atoms in a straight chain, followed by dehydrogenation and introduction of nitrogen therein.

The present process may be carried out by making use of any of the well-known techniques for operating. catalytic reactions in the vapor phase effectively. By way of illustration, butane and ammonia may be brought together in suitable proportions and the mixture vaporized in, a preheating zone. The vaporized mixture is then introduced into a reaction zone containing .a catalyst of the type defined hereinbefore. The reaction zone may be a chamber of any suitable type useful in contact- |catalytic operations; for example, a catalyst bed contained in a shell, or a shell through which the catalyst flows concurseparatlon procedures,

such as pressure stabilization. similarly, the uncondensed hydrogen and unchanged ammonia can be separated from each other. The unchanged butane and ammonia can be recycled with or without fresh butane and ammonia. to the process.

It will be apparent that the process may be operated as a batch or discontinuous process as by using a cataiyst-bed-type reaction. chamber, in which the catalyst .and regeneration operations alternate. with a series of such reaction chambers, it will be seen that as the catalytic operation is taking place in one or more of the reaction chambers, regeneration of the catalyst will be taking place in one or more of the other reaction chambers. correspondingly, the process may be .continuous when we use one or more catalyst I it being clearly understood that the invention is rently, or countercurrently, with the reactants.

The vapors of the reactants are maintained in contact with the catalyst at a predetermined elevated temperature and for a predetermined period' of time, both as set forth hereinbefore, and the resulting reaction mixture is passed through a condensing zone into a receiving chamber. It will be understood that when the catalyst flows concurrently, or countercurrently, with the reactants in a reaction chamber, the catalyst will be thereafter suitably separated from the reacnot to be considered as limited to the specific paraflinic hydrocarbon reactants disclosed therein or to the manipulations and conditions set forth in the examples. As it will be apparent to those skilled in the art, a wide variety of other parafilnic hydrocarbons may be used.

A reactor consisting of a shell containing a catalyst chamber heated by circulating a heat-transfer medium thereover, and containing -100 parts by weight of catalyst comprising 10 parts by weight of vanadium pentoxide supported on 90 parts by weight of activated alumina was used. The catalyst was prepared by soaking commercial activated alumina in an aqueous solution of ammonium vanadate, followed by' heating of the thus treated alumina to drive off water. The catalyst was conditioned by passing a stream of am- Example No 1 2 3 Paramnic Hydrocarbon Reactant Pro ane Butane He 1: 0.

Mol Ratio: Ammonia to Parafiinic Hydrocarbon Reactant.. 221. 3 2 2:1. an

Temperature, F 1,025- 1,050 1,020.

Contact Time, Seconds 4 4 4.

Acetonitrile.

Pr Aoetonitrile Acetonitrile..- Benmnmue Yield per Pass. Percent Weight Based on Parafiinic Hydrocarbon Reactant 3.6.. 3.0.. g a

tion mixtureby filtration, etc. The reaction mixture will be predominantly a mixture of aliphatic nitriles, hydrogen, unchanged butane, and unchanged ammonia. The aliphatic nitriles and the unchanged butane will be condensed in passing through the condensing zone and will be retained inthe receiving chamber. The aliphatic nitriles can be separated from the unchanged It will be apparent that the presentinvention provides an eilicient, inexpensive and safe process for obtaining nitriles. Our process is of considerable value in making available relatively in expensive nitriles which are useful, for example. as intermediates in organic synthesis.

This application is a continuation-in-part of copending application, Serial Number 553,291,

butane by any of the numerous and well known 7 flledBeptembe1-8, 1944, now abandoned.

L Although the present invention has been described in conjunction with preferred embodicontaining at least two and up to about ten carbon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F, and about 1075 F., in the presence of a catalyst comprising a vanadium oxide.

2. A process for the production of nitriles having at least two carbon atoms per molecule, which comprises contacting a paraiflnic hydrocarbon containing at least two and up to about ten car-L bon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of a vanadium oxide supported on a catalyst support.

3. A process for the production of nitriles having at least two carbon atoms per molecule, which comprises contacting a paraflinlc hydrocarbon containing at least two and up to about ten carbon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075" F., in the presence of vanadium pentoxlde supported on alumina.

4. A process for the production 01' nitriles having at least two carbon atoms per molecule, which comprises contacting propane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075" F.,in the presence of a catalyst comprising a vanadium oxide.

5. A process for the production of nitriles having at least two carbon atoms per molecule, which compr'mes contacting propane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of a vanadium oxide supported on a catalyst support.

6. A process for the production of nitriles having at least two carbon atoms per molecule, which comprises contacting propane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F, and about 1075 F., in the presence of vanadium pentoxide supported on alumina.

7. A process for the production of nitriles hav- Number ing at least two carbon atoms per molecule, which comprises contacting butane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F.'and about 1075 F.. in the presence or a catalyst comprisingavanadium oxide. 7

8. A process for the production of nitriles having at least two carbon atoms per molecule, which comprises contacting butane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075" F., in the presence or a vanadium oxide supported on a catalyst support.

9. A process for the production of nitriles. having at least two carbon atoms per molecule, which comprises contacting butane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F'., in the presence or vanadium pentoxide supported on alumina.

' 10. A process for the production of nitriles having at least two carbon atoms per molecule,'which comprises contacting a heptane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of a catalyst comprising a vanadium oxide.

11. A process for the production of nitriles having at least two carbon atoms per molecule, which comprises contacting a heptane with ammonia gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F'., in the presence or a vanadium oxide supported on a catalyst support.

12. A process for the production of nitriles having at least two carbon atoms per molecule, which comprises contacting a heptane with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of vanadium pentoxide supported on alumina.

WILLIAM I. BENTON. I RICHARD B. BISHOP.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date 1,920,795 Jaeger Aug. 1, 1933 1,934,838 Andrussow Nov. 14, 1933 2,331,968 Forney Oct. 19, 1943 2,381,470 Teter Aug. 7, 1945 2,381,471 Teter Aug. '7, 1945 2,381,472 Teter -1 Aug. 7, 1945 2,381,473 Teter Aug. 7, 1945 2,381,709 Apgar et al Aug. 7, 1945 Certificate of Correction Patent No. 2,450,641.

WILLIAM I. DENTON ET AL.

Itis hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 5, line 25, for alefinic read olqfinic; column 6, line 10, for catalyst read catalytic; and that the said Letters Patent should be read wit the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 10th day of May, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

October 5, 1948.

h these corrections therein that 

